CN103151424A - Method for preparing metal electrode on surface of porous silicon by using improved chemical plating process - Google Patents

Method for preparing metal electrode on surface of porous silicon by using improved chemical plating process Download PDF

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CN103151424A
CN103151424A CN2013100776925A CN201310077692A CN103151424A CN 103151424 A CN103151424 A CN 103151424A CN 2013100776925 A CN2013100776925 A CN 2013100776925A CN 201310077692 A CN201310077692 A CN 201310077692A CN 103151424 A CN103151424 A CN 103151424A
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porous silicon
metal electrode
chemical plating
silicon surface
plating process
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CN103151424B (en
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李伟
余峰
王垠
廖家科
郭安然
蒋亚东
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University of Electronic Science and Technology of China
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University of Electronic Science and Technology of China
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Abstract

The invention discloses a method for preparing a metal electrode on the surface of porous silicon by using an improved chemical plating process, and relates to the technical field of semiconductor optoelectronic material and devices. The method comprises the following steps that (1) the surface of the porous silicon is subjected to chemical plating pretreatment; (2) the chemical plating process is adopted; (3) the porous silicon containing the metal electrode is subjected to drying treatment; (4) the porous silicon containing the metal electrode is subjected to rapid annealing treatment; and (5) the metal electrode is etched into a specified electrode shape by adopting the photolithographic process, and the preparation of the metal electrode is finished. On the basis of the special porous surface of the porous silicon, the method utilizes the autocatalysis plating principle of chemical plating to finish the chemical plating of the porous silicon through the improved chemical plating process on the premise that the sensitization activation process is not adopted, so that a layer of metal electrode with good adhesive force and high bonding strength is formed on the surface of the porous silicon, the bonding force of the metal electrode and the surface of the porous silicon is increased, and the contact resistance is reduced.

Description

A kind ofly prepare the method for metal electrode at porous silicon surface with improving chemical plating process
Technical field
The present invention relates to Semiconductor Optoeletronic Materials and device technology field, be specifically related to a kind of preparation method of porous silicon surface metal electrode.
Background technology
From Uhlir in 1956 by since monocrystalline silicon piece being carried out electropolishing and finding porous silicon (Porous Silicon), scholars have just begun the further investigation to porous silicon.Pickering observed the visible photoluminescent phenomenon of porous silicon first at low temperatures in 1984, Canham has at room temperature observed porous silicon high efficiency (〉 1% in nineteen ninety) visible photoluminescent (redness) phenomenon.1996, the people such as Hirschman integrate porous silicon luminescence pipe and planar transistor, have made a photoelectron integrated light-emitting array, and this is the integrated the first of porous silicon photoelectron, be an important breakthrough, show that porous silicon is used for the feasibility of integrated opto-electronics device.These achievements in research show that the opto-electronic device based on porous silicon has broad application prospects.
Traditional silica-base film electrode prepares, and usually adopts the method for vacuum thermal evaporation and magnetron sputtering.But, due to porous silicon surface and inner have a large amount of holes and cone-shaped structure, causing very high porosity and surface density of states, this will greatly reduce the electrical contact performance of porous silicon and metal.For example: 1, the existence of a large amount of holes will make the adhesive force between metal and porous silicon weaken, and cause metal only in the outer surface contact of porous silicon, may produce higher contact resistance; 2, very high surface density of states may cause the pinning effect of surperficial Fermi level, produces the potential barrier of block current flow, causes contact resistance further to increase, and shows rectification characteristic.A large amount of results of study show, by traditional evaporation and sputtering technology, " metal/semiconductor " that be difficult to obtain to have low contact resistance and ohmic contact characteristic contacts.
Contact resistance is low in order to obtain, strong adhesion and stable porous silicon contact with good electric between metal electrode, can the root problem that need to solve be: select new metal electrode depositing operation and material, make that the plated metal particle fully permeates, the hole of filling porous silicon and space, form to reach between metal and porous silicon the purpose that good electric contacts.
Chemical plating is a kind of in the situation that no current passes through, under the effect of metal ion reducing agent in same solution, be reduced into metal by controlled redox reaction having on the plating piece of catalytic surface, thereby obtain the process of metal deposition layer on the plating piece surface, also claim autocatalytic plating or electroless plating.The advantage that chemical plating is the most outstanding is plating piece surface configuration how complicated no matter, as long as solution can obtain the coating of even thickness in deep place, and easily controls thickness of coating.Compare the characteristics that chemical plating has that thickness of coating is even, pin hole is few, do not need DC power supply device, can deposit on non-conductor plating piece surface with plating.
What the present invention relates to is a kind of chemical plating process of improvement, can evenly, stably form the metal electrode that one deck adhesive force is good, bond strength is high at porous silicon surface, electrically contacts quality to improve metal/semiconductor.
Summary of the invention
For above-mentioned prior art, can the technical problem to be solved in the present invention be: select new metal electrode depositing operation and material, make that the plated metal particle fully permeates, the hole of filling porous silicon and space, bond strength between metal and porous silicon is higher to reach, coating difficult drop-off and the purpose that forms good electric and contact.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme:
A kind ofly prepare the method for metal electrode at porous silicon surface with improving chemical plating process, it is characterized in that, comprise the following steps:
1. porous silicon surface chemical plating pre-treatment: at first adopt the HF aqueous solution to remove the porous silicon surface oxide layer, then use washed with de-ionized water;
2. adopt chemical plating process: at deposition layer of metal electrode on the porous silicon surface of 1. chemical plating pre-treatment, described metal electrode composition is Ni-P alloy or Ni-B alloy, and thickness is 0.5 ~ 2 μ m;
3. the porous silicon of containing metal electrode carried out the drying processing;
4. the porous silicon of containing metal electrode carried out the short annealing processing;
5. adopt photoetching process that metal electrode is etched into the appointment electrode shape, complete the electrode preparation.
As further improvement of the present invention: step 1. described in the aqueous solution composition of HF be HF:H 2O=2:1, the reaction time is 10s.
As further improvement of the present invention: step 2. described in the metal electrode composition be the Ni-P alloy, chemical plating fluid consists of NiSO 46H 2O:20g/L, NaH 2PO 2: 30g/L, Na 3C 6H 5O 7: 10g/L and NH 4Cl:30g/L; Described metal electrode composition or be the Ni-B alloy, chemical plating fluid consists of NiCl 26H 2O:25g/L ~ 30g/L, KBH 4: 0.5g/L ~ 3g/L, ethylenediamine 55ml/L ~ 70ml/L; Use at last 28% ammoniacal liquor that chemical plating fluid PH is adjusted to 11, reaction temperature is 35 ℃, and the reaction time is 30min.
As further improvement of the present invention: step 3. described in dry treatment temperature be 100 ~ 120 ℃, drying equipment is electric baking oven.
As further improvement of the present invention: step 4. described in the short annealing treatment temperature be 300 ~ 500 ℃, 30s ~ 1min anneals under argon gas atmosphere.
Compared with prior art, the present invention has following beneficial effect:
One, the present invention utilizes the self-catalysis Principle of plating of chemical plating, chemical plating process by improvement, take the porous area of porous silicon uniqueness as the basis, complete the chemical plating of porous silicon under the prerequisite that does not adopt the sensitization activating process, form at porous silicon surface the metal electrode that one deck adhesive force is good, bond strength is high, can improve adhesion, the reduction contact resistance of metal electrode and porous silicon surface;
Two, the present invention can be used for photodetector and the solar cell based on porous silicon, can improve effectively that device efficiency and response speed and preparation technology are simple, cost is lower.
Description of drawings
Fig. 1 is schematic flow sheet of the present invention.
Embodiment
The invention will be further described below in conjunction with the drawings and the specific embodiments.
A kind ofly prepare the method for metal electrode at porous silicon surface with improving chemical plating process, it is characterized in that, comprise the following steps: 1. porous silicon surface chemical plating pre-treatment: at first adopt the HF aqueous solution to remove the porous silicon surface oxide layer, then use washed with de-ionized water; 2. adopt chemical plating process: at deposition layer of metal electrode on the porous silicon surface of 1. chemical plating pre-treatment, described metal electrode composition is Ni-P alloy or Ni-B alloy, and thickness is 0.5 ~ 2 μ m; 3. the porous silicon of containing metal electrode carried out the drying processing; 4. the porous silicon of containing metal electrode carried out the short annealing processing; 5. adopt photoetching process that metal electrode is etched into the appointment electrode shape, complete the electrode preparation.
Embodiment one is with the preparation method of Ni-P alloy as the porous silicon surface metal electrode of metal electrode.
Step 1: porous silicon surface chemical plating pre-treatment: at first adopt the aqueous solution of HF to remove the porous silicon surface oxide layer, the aqueous solution composition of HF is HF:H 2O=2:1, the reaction time is 10s, cleans with deionized water afterwards.Step 2: chemical plating Mi-P alloy, corresponding chemical plating fluid consists of NiSO 46H 2O:20g/L, NaH 2PO 2: 30g/L, Na 3C 6H 5O 7: 10g/L and NH 4Cl:30g/L.The ammoniacal liquor of use 28% is adjusted to 11 with chemical plating fluid PH, and reaction temperature is 35 ℃, and the reaction time is 30min.Chemical plating cleans up sample, and puts into the roaster drying after finishing with deionized water, baking temperature is 110 ℃.Step 3: short annealing, under 300 ~ 500 ℃ of temperature and argon gas atmosphere condition, annealing 30s ~ 1min.Step 4: adopt photoetching process that metal electrode is etched into the appointment electrode shape, complete the electrode preparation.
Embodiment two is with the preparation method of Ni-B alloy as the porous silicon surface metal electrode of metal electrode.
Step 1: with the step 1 of embodiment 1.
Step 2: Electroless Deposited Ni-B Alloy, corresponding chemical plating fluid consists of NiCl 26H 2O:25g/L ~ 30g/L, KBH 4: 0.5g/L ~ 3g/L, ethylenediamine 55ml/L ~ 70ml/L.The ammoniacal liquor of use 28% is adjusted to 11 with chemical plating fluid PH, and reaction temperature is 35 ℃, and the reaction time is 30min.Chemical plating cleans up sample, and puts into the roaster drying after finishing with deionized water, baking temperature is 110 ℃.Step 3 ~ 4 are with the step 3 of embodiment 1 ~ 4.
Be only below the exemplary embodiment in the numerous concrete ranges of application of the present invention, protection scope of the present invention is not constituted any limitation.All employing conversion or equivalence are replaced and the technical scheme of formation, within all dropping on rights protection scope of the present invention.

Claims (5)

1. one kind prepares the method for metal electrode with improving chemical plating process at porous silicon surface, it is characterized in that, comprises the following steps:
1. porous silicon surface chemical plating pre-treatment: at first adopt the HF aqueous solution to remove the porous silicon surface oxide layer, then use washed with de-ionized water;
2. adopt chemical plating process: at deposition layer of metal electrode on the porous silicon surface of 1. chemical plating pre-treatment, described metal electrode composition is Ni-P alloy or Ni-B alloy, and thickness is 0.5 ~ 2 μ m;
3. the porous silicon of containing metal electrode carried out the drying processing;
4. the porous silicon of containing metal electrode carried out the short annealing processing;
5. adopt photoetching process that metal electrode is etched into the appointment electrode shape, complete the electrode preparation.
2. according to claim 1ly prepare the method for metal electrode at porous silicon surface with improving chemical plating process, it is characterized in that, as further improvement of the present invention: step 1. described in the aqueous solution composition of HF be HF:H 2O=2:1, the reaction time is 10s.
3. according to claim 1ly prepare the method for metal electrode at porous silicon surface with improving chemical plating process, it is characterized in that, step 2. described in the metal electrode composition be the Ni-P alloy, chemical plating fluid consists of NiSO 46H 2O:20g/L, NaH 2PO 2: 30 g/L, Na 3C 6H 5O 7: 10g/L and NH 4Cl:30 g/L; Described metal electrode composition is the Ni-B alloy, and chemical plating fluid consists of NiCl 26H 2O:25 g/L ~ 30 g/L, KBH 4: 0.5 g/L ~ 3 g/L, ethylenediamine 55 ml/L ~ 70ml/L; Use at last 28% ammoniacal liquor that chemical plating fluid PH is adjusted to 11, reaction temperature is 35 ℃, and the reaction time is 30min.
4. according to claim 1ly prepare the method for metal electrode at porous silicon surface with improving chemical plating process, it is characterized in that, step 3. described in dry treatment temperature be 100 ~ 120 ℃, drying equipment is electric baking oven.
5. according to claim 1ly prepare the method for metal electrode at porous silicon surface with improving chemical plating process, it is characterized in that, step 4. described in the short annealing treatment temperature be 300 ~ 500 ℃, 30s ~ 1min anneals under argon gas atmosphere.
CN201310077692.5A 2013-03-12 2013-03-12 A kind of improvement chemical plating process prepares the method for metal electrode at porous silicon surface Expired - Fee Related CN103151424B (en)

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Cited By (4)

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CN103367134A (en) * 2013-08-08 2013-10-23 电子科技大学 Preparation method of porous silicon surface metal electrode based on metal ruthenium decoration
CN104787773A (en) * 2015-04-03 2015-07-22 浙江大学 Erbium silicate with sensitization effect as well as preparation method and application of erbium silicate
CN108486553A (en) * 2018-04-21 2018-09-04 中南大学 Silicon carbide powder nickel plating process
CN111916353A (en) * 2020-07-29 2020-11-10 滁州惠科光电科技有限公司 Display panel and manufacturing method thereof

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103367134A (en) * 2013-08-08 2013-10-23 电子科技大学 Preparation method of porous silicon surface metal electrode based on metal ruthenium decoration
CN103367134B (en) * 2013-08-08 2015-11-11 电子科技大学 A kind of porous silicon surface metal electrode preparation method modified based on metal Ru
CN104787773A (en) * 2015-04-03 2015-07-22 浙江大学 Erbium silicate with sensitization effect as well as preparation method and application of erbium silicate
CN108486553A (en) * 2018-04-21 2018-09-04 中南大学 Silicon carbide powder nickel plating process
CN108486553B (en) * 2018-04-21 2019-11-08 中南大学 Silicon carbide powder nickel plating process
CN111916353A (en) * 2020-07-29 2020-11-10 滁州惠科光电科技有限公司 Display panel and manufacturing method thereof
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CN111916353B (en) * 2020-07-29 2024-05-03 滁州惠科光电科技有限公司 Manufacturing method of display panel and display panel

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